Ice-colors in textile printing with neutral steam



ICE-COLORS IN TEXTILE PRINTING WITH NEUTRAL STEAM Kurt Breig and EugenGlietenberg, Leverkusen-Bayerwerk,

No Drawing. Application December 16, 1954 Serial No. 475,823

Claims priority, application Germany December 28, 1953 6 Claims. (Cl.8-71) The present invention relates to a process of preparing ice-colorsin textile printing and dyeing.

In preparing ice colors in textile printing from diazoamino compounds,thickened caustic alkaline solutions of usual ice-color couplingcomponents and alkali metal Salts of diazoamino compounds containingsolubilizing groups in the radical (stabilizer) not taking part in theformation of the dyestuft", are printed on the fibre and the dyestuff isdeveloped by a treatment with dilute acid or, preferably, withacid-containing steam. This acid treatment involves anumber ofdisadvantages and therefore many attempts have been made to effect thedevelopment of the icecolors solely by applying neutral steam, especially since it is only possible by this kind of development toprepare ice-colors and vat-colors side by side. Thus verysatisfactoryresults could be achieved by reducing the quantity of caustic alkali inthe printing pastes or by adding compounds splitting off acid (cf.applicates Patent tions Nos. 313,582, now Patent No. 2,758,001, 313,583

and 390,084). 7

The ideal case would be, however, dyestufi combinations which can bedeveloped in neutral steam without an addition of compounds splittingoif acid or binding The solution of this problem would therefore alkali.mainly reside in the use of suchdiazoamino compounds which easily andcompletely split up in neutral steam but are completely stable in thecold and'thereby afford a good keeping quality of the printing pastes.The capability of diazoamino compounds to split up greatly de-.

pends upon the basicity of the diazotizable amine on the one side and ofthe stabilizer on the other side. Every diazotized aromatic aminepossesses, depending upon its substituents, a very difierent couplingenergy and forms,

according to whether it is'more strongly or more weakly basic,diazoamino compounds which split up more easily or more difiicultly. Asimilar statement holds true for the-arnines used as stabilizers. It istherefore necessary to: adapt carefully to another amine andstabilizerif a quantitative scissio n of the diazoamino compound is tobe obtained by applying solely neutral steam. The ideal case would be toprovide the suitable stabilizer for each amine; this, however, wouldcause considerable additional costs whentechnically applied.

fWe have now found that the combinations of dihalogeno-alkylordihalogeno-alkoxy anilines Withl-alkylamino-5 (4)-sulfobenzoic acidsrepresent ideal diazoamino compounds for the purpose discussed. Theyyield together with ice-color coupling components when developed withneutral steam very deep and strong prints on cellulosic fibres as wellas a good fixation on staple fibre fabrics from regenerated cellulose.In spite of the easy scission in neutral steam the printing pastesexhibit a very good keeping quality. The prints further Suifer novisible loss in depth of color if printed side by side with vat-colors.Also reducing agents and caustic alkali carried over from vat-colorprinting pastes have no detrimental infiuence upon the development ofthe dyestuffs.

2,822,234 n Patented Feb. 4, 1958 It is important in this connectionthat the new combinations do not decrease in strength under theintermediate rollers in the composite print side by side withvat-colors; this means a special advance over the known combinations. 7

The combinations according to the present invention not only show verygood properties in printing but also prints obtained therewith aredistinguished by general I good properties,in particular by an excellentfastness to light. 7

The following examples illustrate the invention without, however,limiting it thereto.

Example 1 ethoxy-benzene are dissolvedin 50 ml, of alcohol or an- 1'other suitable solvent and 15-20 grams of caustic soda solution of 38 B.in approximately 300 ml. ofwa'te'r and, after'stirring into 500 grams ofthickening agent,

made up with water-to 1000 grams. The printing'paste thus obtained isprinted on' the fibre in customary manner. 1 "After dryingtheprintedtextile material is steamed withneutral steam for about 5-10 minutes,whereby the de-' Afters'oaping at the boil andthe usual removal ofthe'thicke'ning agent, the dyed textileis rinsed and dried. A clearscarlet is obtained which is veryfast to light. Theiprintin'g pastevelopment of the dyestuff takes place.

is of very good keeping quality. The depth of color of the printings onstaple fibi'e fabricis' equal to that of the printings on cotton. Inprinting simultaneously with vat- I dyestuifs, the combination shows onemploying squeezing rollers no decline in the depthof color.

.Example 2 When using according to Example 1 the sodium salt of thediazoamino compound prepared from 1-a1nino-2- stabili'zer described in'Example 1 and 1-acetoacetyl-- amino-4-chloro-2,S-iiirnethoxybenzeneyields on the fibre, 1 after neutral development, a greenish yellowwhich is -methyl-4-bromo-5-chlorobenzene and the stabilizer employed inExample 1, together withithe1-(2'-hydroxycarbazol-3'-carboylamino)-4-chlorobenzene, a full brown isobtained which is very fast to light examples from the sodium salt ofthe diazoamino compoundof 1-amino-3-methyl-4,6-dichlorobenzene with thevery fast tolight. I H

' Exdmp le'4 By replacing the sodium salt of the diazoamino compound ofExample 1 by the sodium salt of the diazoamino compound from diazotized1-amino-4-rnethyl- 2,5-dichlorobenzene and2-isopropylamino-5-sulfobenzoic acid as stabilizer, and using1-(2,3'-hydroxynaphthoylamino)-2-methoxybenzene as coupling component,adding about 10-20 grams of caustic soda solution of 38 B. per kilogramprinting color, a printing paste is obtained which yields on the fibre,after neutral steaming, a strong fast red, the depth of which-on cottonis equal to that on staple fibre fabric.

1 mol of diazotized 1-amino-2-methoxy-4,S-dichlorobenzene is run into asodium carbonate alkaline solution of 1.1 mol of the diso'dium saltofithe' 2 methylamin'o'-5- sulfobenzoic acid, and .the'diazoaminocompound thus formed is salted out witlr so'dium'chlorid'e after" itscom-i plete formation.

60 grams of a mixture consisting of equivalent part'sifof the sodiumsalt of the diazoamino compoundtlius formed and the1-(2,3'-hydroxynaphthoylamino)-2-methoxybenzone are dissolved in about50 ml. of glycol monoethyl ether or another suitablesolvent and.l-20grams Off: caustic soda solution of 38 B.. in approximately 300" ml.of hot water and, after'stirring into'500" grams'of thickening agent,made up' with water to 1000 grams. This printing paste yields, afterneutral steaming, a full bluish redof excellent fastness to light. Thedepth of color on staple fibre fabric is in strength equal to that oncotton.

Example 6 The sodium salt of' the diazoamino compoundof: diazotizedlamino-2amethoxy-4-bromo-S-chlorobenzene and theZ-ethylamino-S-sulfobenzoic acid as stabilizer yields in equivalentmixture with l-benzoylacetylaminoi- 4-benzoylamino-2,S-dimethoxybenzeneunderv the conditions of Example 5, after. steaming in neutral steam,a*-' clear yellow'which. is very fast to light. The. strength of. coloron cotton as well as-on. staplefibre. fabricis" equally deep.

We claim:

1. A process. for printing, textile fibres of the group consisting of'cotton and regenerated cellulose fibers with insoluble azo dyestuffsdeveloped on the fibre whichcom prises diazotizing a compound selectedfrom the group consisting of dihalogeno-alkyl-anilines anddihalogenoalkoxy-anilines, reacting the diazo compound formedwitli acompound selected-from the group consisting of 2- alkali salt with analkali salt of 1-acetyloacetylamino-4- chloro-2,S-dimethoxybenzene,adding a thickener to the mixture, applying the resulting mixture to atextile fiber, and developing the dyestutl onsaid fiber by steaming witha neutralsteam.-

4. A process for printing textile fibers of the group consisting ofcotton and regenerated cellulose fibers with insoluble azo'dyestullsdeveloped on the fiber which comprisesdiazotizing1-amino-2-methyl-4-bromo-5-chlbrobenzene, reacting the diazo compoundwith 2-ethylamino-5- sulfobenzoic acid in the presence of a fixed alkalito form 'an alkali. sali. of a diazoami'no. compound, mixing said alkalisalt with an alkali salt of l-(2'-hydroxycarbazol-3'-car-boylamino)r4echlorobenzene, adding a. thickener tothe mixture,applying the resulting mixture to a textile fiber, anddeveloping-thedyestufi on said fiber by steaming with a neutral steam.

5: A process for printing textile fibers of the group consisting ofcotton and regenerated cellulose fibers with insoluble azo' dye'stufisdeveloped on the fiber which comprises diazotizing lamino-4-methyl-2;S-dichlorobenzene, reacting: the. diazo compound with2-isopropylamino-5-sulfobenzoic acid in the presence of a fixed alkalito form an alka'li salt of a diazoarnino compound, mixing said alkalisalt withan alkali salt of1-(2',3'-hydroxynaphthoyl-a-mino)-2-methoxybenzene, adding a thickenerto the mixture; applying the resulting mixture to a textile fiber,

alkylamino-5-sulfobenzoic acid: and 2-alkylamino-4-sulfobenzoic acid inthe presenceof a fixed alkali to'forrn an alkali saltof. a diazoaminocompound, mixing said alkali salt with an alkali'salt of acouplingcomponent, adding a thickener to' themixture,applyingtheresul'ting mixtureito a textile fibre, anddeveloping thedyestulffonv said fibre by steaming withneutral-steamx 2. A process forprinting textile fibers of the group consisting of cotton andregenerated cellulose fibers with insoluble'azo dyestutfsl developedonthe fiber which? comprises. diazotizing1.-amino-2-'methyl-4,'S-dihlorobenzene, 1

reacting the diazo. compound formedwith- 2sethylarnino S-sulfobenzoicacid in the presence of a fixed alkali to form analkali salt; of: adiazoaminocompoundi-mixing' said alkali salt with an. alkali salt of:1:-(2f,3-hydroxy-' naphthoylamino)-2-ethoxybenzene, adding a thickenerto the mixture, applying the resulting mixture to a textile fiber,and.developingthe:dyestutfsmn said'fiber byfsteaming; with av neutralsteam.

3'. Aprocess for printing-fibers'of'the group'consisting and developingthe dyestufi on said fiber by steaming with a-nentral-steam.

-6.'A process for printing textile fibers of the group consisting ofcottonand regenerated cellulose fibers with yinsoluble'azo dyestuffsdeveloped on the fiber which comprises-r diazotizing1-amino-Z-methoxy-4,5-dichlorobenv zene; reacting the diazo compoundwith Z-methylamino-S- sulfobenzoic acid in the presence of a fixedalkali to form an alkali salt of a diazoamino compound, mixing: 'saidalkali salt with an alkali salt ofl-(2,3'-hydroxynaphthoyl-amino)-2-methoxybenzene, adding a thickener tothemixture, applying the resulting mixture to a textile fiber; anddeveloping the dyestufll on said fiber by steaming-'with a neutralsteam.

References Cited in the file of this patent n UNITED STATES PATENTS882,561

Haller Oct. 11, 1932 2,095,402" Dahlen Sept. 21, 1937 2,338,639, HeatonJan. 4, 1944 2,396,357 Wiest Mar. 12, 1946 2,522,838 Petitcolas Sept. 9,1950 2,675,374 Petitcolas Apr. 13, 1954' 2;158,001' Glietenberg Aug. 7,1956 FOR'EIGN' PATENTS 4975407 Great Britain Dec. 19, 1938' 042,356France" June 3', 1953' 1,056,501 France Oct. 21, 1953'- 4 OTHERREFERENCES.

Chernl Technology of Dyeing and Printingfby L.

Diserens, translated by Wengrafand Baumann, vol. 4;

1. A PROCESS FOR PRINGINT TEXTILE FIBRES OF THE GROUP CONSISTING OFCOTTON AND REGENERATED CELLULOSE FIBERS WITH INSOLUBLE AZO DYESTUFFSDEVELOPED ON THE FIBRE WHICH COMPRISES DIAZOTLZING A COMPOUND SELECTEDFROM THE GROUP CONSISTING OF DIHALOGENO-ALKYL-ANILINES ANDDIHALOGENOALKOXY-ANILINES, RACTING THE DIAZO COMPOUND FORMED WITHALKYLAMINO-5-SULFOBENZOIC ACID AND2-ALKYLAMINO-4-SULALKYLAMINO-5-SULFOBENZOIC ACID AND2-ALKYLAMINO-4-SULFOBENZOIC ACID IN THE PRESENCE OF A FIXED ALKALI TOFORM AN ALKALI SALT OF A DIAZOAMINO COMPOUND, MIXING SAID ALKALI SAITWITH AN ALKALI SALT OF A COUPLING COMPONENT, ADDING A THICKENER TO THEMIXTURE, APPLYING THE RESULTING MIXTURE TO A TEXTILE FIBRE, ANDDEVELOPING THE DYESTUFF ON SAID FIBRE BY STEAMING WITH NEUTRAL STEAM.